Lubricating oils containing metal salts of a condensation product of a substituted phenol and an allyl compound



Patented Oct. 20, 1953 LUBRICATING OILS CONTAINING METAL SALTS OF ACONDENSATION PRODUCT OF A SUBSTITUTED PHENOL AND AN ALLYL COMPOUND LorenL. Neif, Long Beach, Calif., assignor to Union Oil Company ofCalifornia, Los Angeles, Calif., a corporation of California No Drawing.Application July 17, 1950,

Serial No. 174,368

This invention relates to lubricating oil addition agents havingexceptional anti-corrosion and detergent characteristics when added tomineral lubricating oil, and to lubricating oils containing suchaddition agents with and without supplemental detergents. Moreparticularly, the invention relates to oil-soluble metal salts of thecondensation products obtained by condensing hydrocarbon substitutedphenols with allyl compounds as will be described herein and tolubricating oils containing such metal salts.

The ,present trend in internal combustion engines, ;'particularly of thediesel engine type, is in the direction of higher compression ratios,higher operating temperatures and thus higher horse power output perunit weight of the engine. ,Moreover, it is the trend to operate enginesof this type for longer periods without oil change so that oils whichare satisfactory for use in the present-day high output diesel engines,for example, must have not only an initially high detergency andinitially high anti-corrosion characteristics but these properties mustbe retained under severe conditions of use for relatively long periodsof use in an engine. To further complicate the preparation of asatisfactory oil for the lubrication of such engines the fuels availableoften contain higher proportions of sulfur than those Which have beenused in the past and it is well recognized that high sulfur fuels tendto produce'corrosive conditions in an engine which must be overcome bythe lubricating oil employed, otherwise not only does corrosion takeplace in the engine but wear rates are sufficiently high that frequentoverhaul and replacement of parts becomes necessary, thereby undulyincreasing engine operation cost.

In order to prepare oils which may be used in engines of the characterdescribed it has been the practice to merely increase the percentage ofadditive materials which have been used in the past in ordinary dieselengines, automative engines and the like, hoping to gain the extraprotection necessary by the use of these larger pro-- portions.

It is an object of this invention to prepare a lubricating oil whichwill operate satisfactorily in internal combustion engines andparticularly in the high output diesel engines over relatively longperiods of service. It is another object to prepare such lubricatingoils which will protect engines of this type operating under severeconditions even while using a fuel containing as high as 1% or more ofsulfur.

It is found that these and other objects can be obtained by adding tomineral lubricating oil relatively small amounts of an oil-soluble metalsalt of the condensation product of a hydrocarbon substituted phenol andan allyl compound of the type described hereinbelow.

Claims. (Cl. 252--33.4)

Thus the invention resides in lubricating oils containing between about0.05% and about 10% or as high as about 20% by weight of an oilsolublemetal salt of the condensation product obtained by condensing ahydrocarbon substituted phenol wherein the hydrocarbon substituent orsubstituents contain between about 4 and about 30 carbon atoms with anallyl compound of the class consisting of allyl alcohol, allyl ethersand allyl esters of hydrohalogen acids and fatty acids. Thesecondensation products are acidic and capable of reacting with metalbases, as for example, metal oxides, hydroxides and carbonates, underappropriate conditions to form the corresponding metal salts. The termhydrohalogen acids is used herein in its usual sense and includeshydrogen chloride, hydrogen bromide, hydrogen fluoride and hydrogeniodide. These acids may also be termed hydrogen halides.

A typical oil-soluble metal salt is produced by reacting approximatelyone molecular proportion of octyl phenol with one molecular proportionof allyl acetate. The phenol and acetate are dissolved in about 2 partsby volume of a petroleum naphtha and to the solution is added about 2parts by volume of a condensation catalyst, e. g. sulfuric acid. Thecatalyst is added slowly and the temperature of the reaction mixture ismaintained at a point such that the allyl acetate is not vaporizedexcessively. Preferably, the reaction mixture is maintained at atemperature between 60 C. and 72 C. and under these conditions thereaction is found to be complete in about 3 hours. Since the reaction isexothermic, completion of the reaction can be determined by followingthe temperature of the reaction mixture. Thus. whereas during the earlypart of the reaction cooling is necessary in order to maintain thetemperature within the desired range, toward the end of the reactionheat may be necessary in order to maintain this temperature. Followingthe completion of the reaction the product is cooled and water washeduntil free of mineral acid. Upon evaporation of the solvent naphthaemployed there remains a resinous material having a dark brownish color.The resin may be converted into its metal salt, as for example thebarium salt, by treatment of a solvent solution, as for example anaphtha or a hydrocarbon lubricating oil solution, of the resin withbarium hydroxide octa-hydrate or with anhydrous barium hydroxide, inwhich latter case it is necessary to add small amounts of Water duringthe neutralization. Where the metal salt is the desired product, thesolvent solution of the condensation product is mixed with the desiredmetal base and, after neutralization and elimination water, the solventis evaporated leaving the metal salt of the condensation product. Thebarium salt of the above condensation product is a semisolid to solidresin of brownish color. Where it is desirable to prepare a lubricatingoil concentrate of the metal salt of the condensation prod.-v uct theneutralization is preferably effected in mineral oil solution. In thiscase the condensation product or the solvent solution -of the con-vdensation product is dissolved in about 1 to about volumes of minerallubricating oil and the desired metal base and Water is added Theresulting product is agitated and heated sufficiently to effect completeneutralization and subsequently filtered to remove solid impurities. Theresulting product will be referred to as an oil concentrate of anoil-soluble metal salt of the. gondensa tion product of a hydrocarbonsubstituted phenol and an allyl compound of the class described.

gHyd'rocarbo'n substituted phenols which are .usefulin the preparationof the oil-soluble metal ts of this invention include the phenolshavalkyl, cyc'loalkyl, 'aryl, aralkyl and alkar y'l ituents. The.substituents may be in the ,e ho., metaor para.- positions. Preferablythe b mpo'und will have either an orthoanda para- .p itio'n free ofsubstituents, or if the para-posi- (ti n 'isqsubsftituted thenpreferably both orthoiaos'itiiiii's should be free of substituents.Alkyl increments "include the butyl, amyl, iso-amyl', h'xyl, heptyl,.octyl, .Iauryl, .cetyl and like radi- "The'se radicals may'be normal orbranched groups and thephenol may contain one or ji ore thesesubstituents. Moreover, the alkyl substituent's inelude, the .so-calledwax radicals, he. radi s "derived from paraflin wax which may contanasjhigh as or more carbon atoms... wax 'phe'nolsare. well known in theart Jand lmaybe prepared by reacting phenol with ;1nated.parafi in,.wax.in the presence of a E (Kiel-( Shaftv Catalyst. Cycloalkyl substituentsincludecyclohexyl, .methylcyclohexyl, cyclopeninmates/ ethyl and propylcyclopentyl radicals and the like. ,Aryl radicals include the phenyl frdic'al, 'asifor example ,phenyl phenol. Aralkyl if icals "include the.benzyl radical and thus .benjzyl phenol. Alka'ryl radicals. include thefradicals such as methylphenyl, 'ethylphenyl and theflik v 'Allylcdnp'ounds which are'useful in preparing the condensation products.include allyl aljc'ohol, the lower molecular weight allyl ethers',asffoifljexallilple diallylljether, allyl ethyl Ethel,

allyhpropyl'ether andthe like and aim esters.

J1 egau'yl' esters, include 'the..allyl hydrohalogen ,e'cm esters, "asfor. example allyl .ehlor'ide, allyl hr mide and auy iodideand..thejlowerQmoleom is ightcarboxyiic acid esters,- particularly VtyQacid esters, as. forfexample allyl acerate; llyl 'propiona'te, allylbutyrate and thelike. Generally the carboxylic or. fatty acidfradica fpL t in the. ester will contain '1.to..5 .or 6 .carbon atemfs. andpreferably 2.700. '4 carbonatoms. The 'molar ratio of. hydrocarbonsubstituted .phenol- .tb allylf compound to be ,used in preparing sesamecondensation products will be between laboutl..0.5.. and about 3 to l.Preferably this rat i0 Will fall between. about 0.8 and about jzg'tljParticularl satisfactory results. have been obtained. usingapproximately equal .molecular fproportions of phenol andallylcompound.Catalystsfor condensation agents which may .be employediand which servetoeiiect the de- .s ired condensation reaction include the acidcatalysts si m l f ri aci nd. P 195." Jphoric .a idas Well as h e Q -Cmt ty .catalysts. i udin um num chl i e, boron trifluoride, zinc.chloride and; the like. In the case of boron trifiuoride, this compoundis generally employed in the form of its complex with .diethyl ether.The complex is known as boron trifiuoride etherate and has a boilingpoint of about C. The amount of catalyst to be employedwill generally bebetween about 0.5% and 10% "by weight of the total reactants. However,as much as 20% may be employed if desired, with satisfactory results.

Although the condensation reaction will take place in the absence ofsolvent or diluent, it is generally desirable to employ a solvent duringthe-condensation reaction. Solvents which may be employed include thosewhich do not react with phenols or with the allyl compounds under theconditions of condensation, Such solvents include the hydrocarbonnaphthas or thinners, aromatic solvents, as for example benzene,toluene, and xylene, and the like as well as chlorinated solvents suchas chloroform, carbon tetrachloride and the like. Also, the condensationis satisfactorilyv effected using mineral oil as the :solvent ordiluent. Thus, the solvent can be the .oil to be used in the preparationof the final lubricating oil composition. The amount of solvent ordiluent to be employed may be widely varied, although generally between0.5 and 5 ,volumes of solvent per volume of reactants is 'found to. givesatisfactory results. v

The temperature of reaction will depend upon the reactants involved butwill generally be between about -20 C. and about 200 C. and preflerablybetween about 0 C(and about 100 C. or C. The temperatureemployed willdepend 'to some extent upon the volatility of the allyl compoundemployed and also. upon the reactivity of theallyl compound. With themore volatile compounds, as for example allyl chloride, lowertemperatures are generally preferred and pressures up to 3 or ,4atmospheres may be employed .if desired in order to maintain thereactants in ,solution or in liquid condition at the temperaturesemployed. ,7

The time of reaction is dependent upon the ,'particular reactants. andupon the temperature ,and condensation agentemployed, although generallyit is found thatfbetwjeen about 1 hour'and e'or '5'hours. suffices toeffectthe desired extent of condensation. However, entirely satisfactorycondensation products, have been prepared when the reaction conditionswere maintained for as long as 24 hours. Products soobtained are found.to be oil-soluble. and metal salts derived from the condensationproducts. are also oil-soluble.

The lnietals tobe employed in preparing metal salts, of the condensationproducts are preferably. the polyvalent metals, although the monovalentalkali; metals are satisfactory .in some instances. Thus the sodium,potassium and lithium salts are found to be oil-soluble and have thedesired characteristics when added "to mineral lubricating oils. Of the.polyvalent metals, thealkaline. earth lmetals calcium, magnesium, bariumand'strontium are particularly elfective. However, the zinc, lead andaluminum salts are suitable andin somecases chromium, iron, nickel,cobalt, mercury, tin and other polyvalent metal salts have utility and,are to be considered part of this invention, although'this latter groupofpolyvalent metal salts are not to be considered equivalent to thealkali and alkaline earth metals and zinc, lead and aluminum salts..Inbr paring; metal. salts of the acidic condensation products a solventsolution ora lubricating oil solution of the condensation productproduce outstanding lubricating oils.

5 is heated with the desired metal base, i. e. oxide, hydroxide orcarbonate, in the presence of a small amount of water or in the presenceof a small amount of alcohol. The mixture is agitated and heated toeliminate water and effect neutralization. In the case of the moreweakly basic metal the metal salt is preferably made by a methodinvolving first preparing the alkali metal salt, as for example thesodium salt, and subsequently metathesizing the alkali metal salt withan inorganic salt of the desired metal. This metathesis is carried outin alcoholic solution in order to prevent hydrolysis which would occurin aqueous solution. Methods of metathesizing weak acid salts are wellknown in the art and therefore need no further description here. Thissame method of preparation may be employed in producing any of thepolyvalent metal salts if so desired.

the oil containing the metal salt to a temperature of 100 C. to 150 C.and agitating the solution to effect rapid and complete solution and/ordispersion. Lubricating oils which may be employed include substantiallyall types of mineral lubricating oils. Thus the oil may be one having aviscosity index of or even lower or it may be a 'paraflinic type oilhaving a viscosity index in the neighborhood of 100. Particularlysatisfactory results have been obtained using a solvent treated Westernparaffinic mineral lubrieating oil having a viscosity index of betweenabout 85 and 95.

Although lubricating oils containing the additive of this invention asthe only additive material are particularly effective, it is often de---'sirable, particularly where the oil is to be used under severeservice conditions, to incorporate in theoil relatively small amounts,as for example 0.5% to 8 or 10% by weight, of a supplemental detergent.It is found, for example, that oil-soluble metal sulfonates andparticularly the oil-soluble metal salts of mahogany sulfonic facidsobtained by treating lubricating oil fractions of petroleum withsulfuric acid, $03 or chlorosulfonic acid, which methods of preparationare well known in the art, appear to cooperate with the additives ofthis invention to Thus by adding between about 0.5 and 5% by weight of ametal petroleum sulfonate it is found that the detergency of the oil isimproved without adversely aifecting the anti-corrosion or antioxidationcharacteristics of the oil.

Another detergent which appears to cooperate with the additives of thisinvention is a modified sulfonate prepared by heating an oilsolublemetal petroleum sulfonate with an inorganic base to solubilize the basein the sulfonate. Thus, mahogany sulfonic acids may be reacted withinorganic bases as, for example,

with metal oxides, hydroxides, carbonates and Cir indicates a completelyclean engine. volume of carbon present in the top ring groove 6 andthese materials are found to impart 'excep tional detergencycharacteristics to lubricating oils containing the condensation productsalts of this invention. Such oil-soluble complexes of sulfonic acidsand metal hydroxides, oxides, carbonates and the like which may beemployed together with the additive of this invention are thosedescribed by Mertes in U. S. Patents Nos. 2,501,731 and 2,501,732.

The metals to be employed as constituents of the sulfonate or modifiedsulfonate supplemental detergents are the same as those describedhereinabove as being useful as constituents of the condensationproducts.

Two different engine tests have been employed in the evaluation oflubricating oils containing the oil-soluble metal salts of thisinvention. These tests have been carried out in Lauson single cylinderengines and a single cylinder Caterpillar Diesel standard test engine.The tests are referred to as the Lauson engine test and the Caterpillartest, respectively.

Tests in the Lauson single cylinder test engines are carried out in sucha manner that the oil is subjected to severe service conditions. Thistest is employed to determine the corrosion tendencies of the oil and todetermine the tendency for the oil to deposit resinous and lacquer-likematerials in the engine. In carrylllg out the Lauson engine test theengine is operated for a total of 60 hours under a load of about 3.5horsepower, with a coolant temperature of about 295 F. and an oiltemperature of about 280 F. At the end of the test the cleanliness ofthe engine is observed and the oil is given a numerical detergencyrating between 0% and where 100% indicates aperfectly clean engine.Thus, a detergency rating of 100% would indicate that during the testwith a given oil there were substantially no lacquer or varnish-likedeposits within the engine. The corrosivity of the oil is measured bydetermining the loss in weight of corrosion-sensitive copperleadbearings during the period of test. Generally, the bearings are removedand weighed after 20, 40 and 60 hours of operation.

In those cases in which corrosion is extremely severe and there appearsto be danger of engine failure due to excessive corrosion of thebearings asindicated by an examination made at the 40-hour period, thecopper-lead bearings are replaced with babbitt bearings in order tocomplete the 60-hour test. The results of such engine tests are shown inconnection with some of the examples presented hereinbelow. I

In the Caterpillar test which is employed to determine the detergency ofan oil, i. e., the ability of the oil to prevent lacquering of theengine, the engine is operated for a period of 240 hours under a load ofabout 19.8 horsepower with a coolant temperature of about 175 F. and anoil temperature of about 145 F. The fuel employed is a diesel fuelcontaining 1% by weight of sulfur. After hours and at the end of thetest a numerical detergency rating" is as-.- signed. The method ofrating is similar to that employed in the Lauson engine test and 100%Also the behind the ring is determined and this result is expressed atper cent by volume of the space behind the top ring at the start of thetest.

The following examples illustrates some modifications of the invention,however it is to be realized that various modifications of the de- 7scribed methods of preparation and thedescribed condensation product:salts'come within the scope of. the invention.

Example I ,A 206 g. portion of octylphenol 'is'dissolved in 1500 m1, of.alight paraifinic' naphtha boiling in the range 60-100 'C. and to thissolution. is added 68 ml. of allyl alcohol. This mixture is placed in'ailask; equipped with a. stirrer,- thermometer and reflux-condenser.

Sulfuric acid .(98% concentration) is added drop-wise through the refluxcondenser untila total of 54 ml. has been added. During the initialaddition the temperature rises to apoint of rapid reflux (about 72C.),and the addition is continued at a rate such that refluxing continues.Eollowing the addition of the sulfuric acid ,the mixture is heated atits reflux temperature for hours and then cooled. washed with wateruntil free of acid and then heated to 125 C. to evaporate the naphtha. A75 g. portion of the product is dissolvedin 925 g. of an SAE 30 solventextracted Western mineral lubricating oil by heating to 140 C. withstirring. To this solution is added 56 g. of anhydrous barium hydroxideand'150 ml. of water. The water is added drop-wise at 140 C. Theresulting mixture is heated to 175 C., and filtered while hot using afilter aid. This product is an oil concentrate. containing approximately12% by ,weightoi the barium salt of the condensation product ofoctylphenol with allyl alcohol. This product without further dilutionoperates satisiaetorilyin a Lauson engine, giving a high detergency andvery low bearing weight losses.

A lubricating oil is prepared by dissolving 32 partsby weight of theabove oil concentrate and about. 3.7 parts by weight of an -oilconcentrate of calcium petroleum sulfonate in 64.3 parts by I weight ofthe same SAE 30 mineral lubricating oil described above. The resultingoil containing approximately 3% by weight of the barium salt and havinga calcium sulfate ash due to calcium sulfonate of approximately 0.24%istested in a Caterpillar engine as described above, using a fuel.containing 1% of sulfur. This oil has a detergency rating of over 95% at240 hours.

In comparison, the base oil without additives cannot be tested in thisengine using a 1% sulfur .fuel for the reason that the deposits are sogreat as to. cause piston and ring sticking. at far less. than 120 hoursto such an, extent that it is impossible to complete thetest. Thebaseoil, i. e.

the oil withoutadditives, run in the same engine using a low sulfur.fuel has a detergency rating of. approximately 55% at 120 hours. V

Tests on the base oil, on the oil concentrate as produced'abovaand onthe oil prepared for testing in the Caterpillar test engine are asfollows:

, =a g. (.1, mol)- portion of p-octylphenol' and .25 (0.2 mol) of borontrifiuoride etherate'are dissolved in 1 liter'of light petroleumnaphtha.

The product is L The solution is placed in afiask fitted with-arefluxcondenser and maintained at"about"26". To this solution, 81.5 ml.v(Imol) ofallyl chloride is added slowly'with stirring. Thetemperaturedoes not change'upon addition of the chloride but the solution darkens.The mixture'is heated at its reflux temperature; about 67C., for 8.5hours. During this heating HCl is'evolved.

"The product is washed free of mineral "acid with water, evaporated toeliminate the naphtha and chilled with'ice whereuponcrystalsiofflunreacted octy lphenol form. The crystallized phenol isremoved by filtration. Vacuum distillation' of the filtrate removesadditional quantities of unreacted phenol. The'bottoms fraction from thedistillation, consisting of'the condense.- tion product'ofoctylphenol-vinyl chloride condensation product, is a clear brownresinous material.

The above condensation product isxconverlted into. its barium salt bydissolving 7.5 'pai'tsby weight of the condensation product in92.5"parts by weight of the lubricating oil described in 'Example I andadding the equivalent amount of barium hydroxide, together with asmall'amount of water. The mixture is heated to 175 C. and filteredusing a filter aid to yield an oil concentrate of the barium salt ofoctylphenol-vinyl chloride condensation iproduct'having 'a soap numberof 3.77 mg. KOH/g.

A lubricating oil containing'20%.'by weight of the above oil concentrateand by weight of an SAE 30 solvent refined'pa'rafiinic'lubricating oilhas good detergency and anti-corrosion characteristics as shown byLausonenginel tests.

Eromple in To a mixture of 440g. of p-nonylphenol and- 144 g. of allylacetate is added 54 ml. of 98% sulfuric acid. The acid is added slowlywhile-maintaining the reaction mixture at about 25 C. by externalcooling. The reaction mixture is maintained at this temperature withstirring'for 3' hours and then dissolved in 1.5 liters of lightpetroleumnaphtha and the solution water washed to remove free mineral acid. Anoil solution of the condensation product is-"prepared lay-dissolving thenaphtha solution in 3500g. of mineral lubricatingoil of the typedescribed in Example 'I'and topping the mixture to C. to remove thenaphtha.

Approximately one-third of the above-oil solution is treated. with 164g. or lead" oxideand 150 ml. of water- The mixture is gradually :heatedto C. and filtered hot through filter aid' to obtain as filtrate anroil:concentrate of the lead salt of nonylphenol allyl *acetateconden'sationproduct.

The remaining 'two thirds of'the oil-solution of condensation productisneutralized with 59g. of sodium hydroxide in the form of a 25% aqueoussolution. The mixture isgra'dual-ly heated to 200 C. and filtered hotusing afil'ter aid" to obtain as filtrate an oil concentrate ifthe'sodium'salt ofignonylphenol-allyl'acetate condensation 'producApproximately" one-half of the "oil concentrate of the sodium" saltproduced as indicated in the preced'ing'paragraph is diluted vvith 3liters of -7.0 petroleum naphtha andtreat'ed'with a solution of100'g. ofanhydrous zinc chloridein 600ml. 'of isopropyl alcohol. The mixture isstirred for "3 hours and then topped to remove the'alcoh'ol and naphtha.The topped material "is filtered to remove solids and consists of anoil' concenadded 108 ml. of allyl acetate. added slowly with stirringand the temperature 9 trate of the zinc salt of nonylphenyl-allylacetate condensation product.

Oil concentrates of each of the three metal salts produced as describedabove incorporated in additional quantities of the same lubricating oilto give oils containing 3% by weight of the metal salt in each instanceimpart detergency and anti-corrosion characteristics to the oil.

Example IV To a mixture of 175 g. of o-cyclohexylphenol and 112 ml. ofallyl ethyl ether in 1.5 liters of naphtha is added 54 ml. ofconcentrated sulfuric acid. The sulfuric acid is added slowly withstirring and the mixture is refluxed at a temperature of about 80 C. for4 hours and then water washed to remove free mineral acid. The resultingnaphtha solution of condensation product is dissolved in 1000 g. ofmineral lubricating oil of the type described in Example I and to thissolution is added 46 g. of lithium hydroxide monohydrate and 100 ml. ofwater. The resulting mixture is heated gradually with stirring to 175 C.and filtered to obtain as filtrate an oil concentrate of the lithiumsalt of cyclohexylphenol-allyl ethyl ether condensation product.

A lubricating oil prepared by dissolving by weight of the above oilconcentrate in additional quantities of the same mineral lubricating oilused in the preparation of the concentrate has a detergenoy above 88% inthe Lauson test engine and a bearing weight loss of less than 400 mg. at60 hours.

Example V To a solution of 170 g. of p-phenylphenol and '38 ml. of borontrifluoride etherate in 2 liters of light petroleum naphtha maintainedat C. is The acetate is and neutralized with 41 g. of calcium hydroxideusing 100 ml. of water. The mixture is gradually heated to 175 C. andfiltered hot to obtain as filtrate an oil concentrate of the calciumsalt of phenylphenol-allyl acetate condensation prodduct. Thisconcentrate may be employed as a lubricant for internal combustionengines and 'furnishes exceptional protection to the engine.

Example VI A paraffin wax having an average molecular weight of about350 is treated with gaseous chlorine to obtain a. chlorinated parafiinwax containing approximately one atom of chlorine per molecule of thewax. This product is condensed with phenol in the presence of anhydrousaluminum chloride to obtain a wax substituted phenol having a molecularweight of approximately 450.

About 900 g. of the wax substituted phenol prepared as just described isdissolved in 1000 g. of an SAE' 10 solvent refined mineral lubricatingoil and the mixture heated to 40 C. To this solution is added 102 ml. ofallyl alcohol and 54 ml. of concentrated sulfuric acid is added slowlywhile maintaining a temperature between 40 C. and C. This temperature ismaintained for a period of about 5 hours and the mixture water washed toremove mineral acid.

To approximately one-third of the above oil solution of wax phenol-allylalcohol condensation product is added 231 g. of barium hydroxideoctahydrate and the mixture heated to 175 C. and filtered to obtain asfiltrate an oil concentrate of the barium salt of wax substitutedphenol-allyl alcohol condensation product. A lubricating oil containing10% by weight of this oil concentrate in an SAE 30 mineral lubricatingoil having a viscosity index of 55 operates satisfactorily in the Lausontest engine.

The remaining two-thirds of the oil solution of condensation productproduced as above described is neutralized with potassium hydroxideusing 82 g. of KOH in the form of a 50% aqueous solution. The mixture isheated to 200 C. and filtered hot to obtain as filtrate an oil solutionof the potassium salt of a wax substituted phenolallyl alcoholcondensation product.

To approximately one-half of the oil concentrate of the potassium saltdescribed in the preceding paragraph is added one liter of petroleumnaphtha and a solution of 95 g. of nickel chloride in one liter ofisopropanol. The mixture is agitated vigorously for 3 hours and thenheated to 150 C. to vaporize naphtha and isopropanol and filtered toobtain as filtrate an oil concentrate of the nickel salt of a waxsubstituted phenol-allyl alcohol condensation product. This concentrate,when added to mineral lubricating oils in amounts between 5% and 15% byweight, imparts detergency and anti-corrosion characteristics to theoil.

Example VII To a mixture of 305 g. of m-pentadecylphenol and 119 m1. ofdiallyl ether is added 5.4 ml. of

concentrated sulfuric acid. The acid is added slowly while maintaining atemperature below about 150 C. This temperature is maintained for aperiod of approximately one hour. The reaction product is dissolved inone liter of naphtha and washed free of mineral acid with water.

To approximately one-half of the naphtha solution prepared as above isadded 23 g. of lithium hydroxide monohydrate and 10 ml. of

water and the mixture is refluxed for 3 hours.

At this time a water trap is placed in the reflux line and refluxingcontinued until no further quantities of water are recovered in thewater trap. The product is cooled and filtered and the filtrate toppedto C. to remove naphtha and leave the lithium salt ofpentadecylphenol-diallyl ether condensation product.

To the remaining one-half of the naphtha solution of condensationproduct produced as above is added 1500 g. of the lubricating oildescribed in Example I and to this oil solution is added 16 g. offreshly precipitated magnesium hydroxide and 20. ml. of Water. Themixture is heated to C. and filtered hot using a filter aid to obtain asfiltrate an oil concentrate of the magnesium salt ofpentadecylphenol-diallyl ether condensation product.

Lubricating oils containing, respectively, 2.5% by weight of the abovelithium salt and 11% by weight of the oil concentrate of magnesium saltare found to have exceptional detergency and anti-corrosioncharacteristics as shown by Lauson engine tests.

It is to be pointed out that the preceding examples are illustrative ofthe invention and are not to be considered as limiting because thephenols having one or more of the other hydrocarbon substituentsdescribed herein and other allyl compounds described herein are found toconamsegen dense under similar" conditions to formz come parable"condensation products; Moreover, :the other metals described herein asbeing" useful; in preparing the metal salts 'of the-condensationproducts maybe substitutedIfor=thef metals em ployed' in the examples togive-salts which; ".21 6 effective as detergents andanti-:corrosion1:agents when added to mineral lubricatingcoilsz Iclaim:

1. A mineral'lubricating oil containing-she tween about 0.05 and.- about20%rby'weight"of an' oil-soluble metal sa'lt of the acidic condensa tionproduct of 1 a hydrocarbon substituted phenot; in "which the:hydrocarbon substituent con-'- tains between about l and a'boutiio:carborratoms, and an' allyl" compound selected from: the classconsisting of allyl alcohol; diallyl ether; allyl ethyl ether,allyli-propyl ether, allylestersof hydrohalogenacids and allyl estersofzfatty acids containing between 1 and t6 carbon atoms in the fattyacidradical, saidcondensatiorrproduct' be; ing :obtained by condensing'saidrphenolzwithfisaid allyl compound'in' themolarwratio of betweenOfrand '3 to 1 at=-temperatures -between.- about -20 C.and:about=l5.0C'.-

2; A- mineral lubricatingwilt-containing.be tweeri about005 and=about20%- -by weight of anoil-soluble alkaline earth metal' salt of theacid-ic'condensati'on product of a hydrocarbon substituted phenol, in 1which thehydrocarbon substituent' contains between about 4 and about 30carbon atoms, and an allyl compoundz'selected from the classconsistingsof-allyl alcohol, allyl ether, allyl ethyl ether, allylpropyl ether, allyl esters of hydrohalogen .acids and allyl esters offatty acidsicontainingJbetween 1 and6 carbon atoms in the fattyiacidradical, said condensation product being obtained "by condensing saidphenoLwith said allyl compound in the molar ratio of between 025 .and'Sto' 1" attemperatures between about'0 C. and about "100'"'C.1

3. A mineral lubricating" oil containing be tween about 0.05 and about.20% by weiglifof an oil solublealkali metal salt ofth'e'a'ci'diccondensation product ofa hydrocarbon substituted phenol in whichthe hydrocarbon substit'uent contains between about 4": and" about '30carbon atoms and an allyl compound selected from the. class consistingof allyl alcohol; allylfetli'er, allyl ethyl ether, allylLpropyl ether,allyl esters of hydrohalogen' acidsandiallyl esters of fatty acidscontaining between 1 and 6 carbon atoms in the fatty acid radical,saidtondensation prod: uct being obtained by condensing saidI phenolwith said allyi compoundin the molar" ratio of between 0.5'-andf3 to..1; at' temperatures between about-20C. and about 15s c:

.4; Amineral lubricatingoil according to claim 11 in which themolar-ratio of phenol to allyl compoundis between 0.8"an'd' 2 to 1.

,A mineral lubricating .oil according 'ito 'claim 2 ,intwhichsaid'alkaline earth metal'salt is a barium salt.

6. A mineral lubricating oil'according to claim 2.in which said alkalineearth metal salt is a calcium salt.

'7. A lubricating oil according to claim 3 in which said alkalimetallsalt is a lithium salt.

lubricating oil according to claim 3. in which said alkali metal salt?isa;sodiumisalt;

9 A: mineral lubricating oilpcontainingbetween about 0.05 and-about 20by weight of an oil-' soluble .tmeta'l salt ofvtthe acidic reactionproduct obtainedi by condensing at a temperature F138- tween' 0 C and.C.'a hydrocarbonrsubstituted phenol inawhich: the hydrocarbon;substituent contains between about .4 and about 30 carbon atoms withallyl acetate using a molar ratio of phenol to allyl'acetate of between018' and i-Z' to 1.

10 A mineral lubricating oil containing between'about'0.05% and about20% by weight of oil-soluble metal'salt of the acidic reaction productobtain'ed' by: condensing a hydrocarbon substitutedphenol in wh'ich'thehydrocarbon substituent' contains 'between about 4 and about T30carbonfi-atoms with allyl alcohol using a:molar ratio of phenol to.allyl alcohol of between 0.8 and 2"to 1, the condensation being:efiected :at temperatures between: 0 C. and 100 C.

11-. A'-. mineral lubricating oil containing: be tweenab'out 0.05:'and'.about"20% by'fweight of an oil-soluble m'etallsalt of the acidic:reaction product obtainedbycondensing a; hydrocarbon substituted phenolin' which the hydrocarbon-sub stituent contains between about42andiabout 30 carbonatoms'withzallyl chloride, atra-zltemperature'betweenabout 0 C. and about100"C., using amolar. ratio'aof iphenottoallylchloride: between 0&8 andi2ft'ml.

12." mineral lubricating: oil 2 containing "be; tween about 0.5% andabout 10% by weight of the barium salt of the: acidic icondensationproduct obtained by-condensing at temperatures-between about 0 CQ-andabout 100 0;, -approximately equal molarproportions ofi'analkyllsubsti'tuted phenol and allyl aceta'te, the alkyl substituent ofsaid-phenol containingbetween about 4iand about 30 carbon atoms.

13. A mine'ral lubricating oil containing. between about 0.5% and about10%' b"y. weight of thebarium sa'lt'of the acidic condensation prodnotobtained 'by condensing.approximately equal molarflprop'ortions of-.octylphenol and allyl alcohol at temperatures between about 0C; andabout 100 CV '14; A mineral lubricating oil accordingito claim 1containing also between" about 0.5" and about '10 by. weight of anoil-soluble --meta1 sulfonate.

"151 A mineral lubricating .oil according to claim 1' containing alsobetween05 and"1'0% of a modified sul'fonateprepared by"heati ng anoil-soluble" metalsulfonate with an inorganic base selected from theclassconsisting of metal oxides, hydroxides, carbonates and bicarbonatesto solubilize said base, said modified sulfonate having a. ratio ofequivalents ofmetal-to equivalents of sulfonicracidsbetween 1.1 and 3 tol.

LOREN L. NEFF;

ReferenceaCitedin the file of this patent UNITED STATES- PATENTS

1. A MINERAL LUBRICATING OIL CONTAINING BETWEEN ABOUT 0.05 AND ABOUT 20%BY WEIGHT OF AN OIL-SOLUBLE METAL SALT OF THE ACIDIC CONDENSATIONPRODUCT OF A HYDROCARBON SUBSTITUTED PHENOL, IN WHICH THE HYDROCARBONSUBSTITUENT CONTAINS BETWEEN ABOUT 4 AND ABOUT 30 CARBON ATOMS, AND ANALLYL COMPOUND SELECTED FROM THE CLASS CONSISTING OF ALLYL ALCOHOL,DIALLYL ETHER, ALLYL ETHYL ETHER, ALLYL PROPYL ETHER, ALLYL ESTERS OFHYDROHALOGEN ACIDS AND ALLYL ESTERS OF FATTY ACIDS CONTAINING BETWEEN 1AND 6 CARBON ATOMS IN THE FATTY ACID RADICAL, SAID CONDENSATION PRODUCTBEING OBTAINED BY CONDENSING SAID PHENOL WITH SAID ALLYL COMPOUND IN THEMOLAR RATIO OF BETWEEN 0.5 AND 3 TO 1 AT TEMPERATURES BETWEEN ABOUT -20*C. AND ABOUT 150* C.